Merocyanine derivatives for cosmetic use

ABSTRACT

The use is described of merocyanine derivatives of formula (1), wherein R 1  and R 2  are each independently of the other hydrogen; C 1 -C 22 alkyl; cyclo-C 3 C 8 alkyl; or unsubstituted or C 1 -C 5 alkyl- or C 1 -C 5 alkoxy-substituted C 6 -C 20 aryl; orl; or R 1  and R 2  together with the nitrogen atom linking them form a —(CH 2 ) m — ring which is uninterrupted or, interrupted by —O— or by —NH—; R 3  is a cyano group; —COOR 5 ; —CONHR 5 ; —COR 5 ; or —SO 2 R 5 ; R 4  is a cyano group; —COOR 6 ; —CONHR 6 ; —COR 6 ; or —SO 2 R 6 ; R 5  and R 6  are each independently of the other C 1 -C 22 alkyl; or unsubstituted or C 1 -C 5 alkyl substituted C 6 -C 20 aryl; or R 3  and R 4  together or R 5  and R 6  together form in a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; Z 1 , and Z 2  are each independently of the other a —(CH 2 ) n — group which is uninterrupted or interrupted by —O—, —S—, or by —NR 7 —, and/or is unsubstituted or substituted by C 1 -C 5 alkyl; R 7  is (C l C 5 alkyl; 1 is from 1 to 4; m is from 1 to 7; n is from 1 to 4; when n=2, R 1 , R 5  or R 6  is a bivalent alkyl group; or R 1 , and R 2  together with the 2 nitrogen atoms linking them form a —(CH 2 ) m — ring; when n=3, R 1 , R 5  or R 6  is a trivalent alkyl group; when n=4, R 1 , R 5  or R 6  is a tetravalent alkyl group; and R 1 , and R 2  in formula (1) are not simultaneously hydrogen, in protecting human and animal hair and skin from UV radiation.

The present invention relates to the use of merocyanine derivatives in protecting human and animal hair and skin from UV radiation and to cosmetic compositions comprising such compounds.

The compounds for use in accordance with the invention correspond to formula

wherein

-   R₁ and R₂ are each independently of the other hydrogen; C₁-C₂₂alkyl;     cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C₆alkyl- or     C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ together with the     nitrogen atom linking them form a —(CH₂)_(m)— ring which is     uninterrupted or interrupted by —O— or by —NH—; -   R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; —CONR₁R₆; -   R₄ is a cyano group; —COOR₆; —CONHR₆; —COR₆; or —SO₂R₆; —CONR₂R₆; -   R₅ and R₆ are each independently of the other C₁-C₂₂alkyl;     cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C6alkyl-substituted     C₆-C₂₀aryl; -   or R₃ and R₄ together or R₅ and R₆ together form a 5- to 7-membered,     monocyclic, carbocyclic or heterocyclic ring; -   Z₁ and Z₂ are each independently of the other a —(CH₂)₁— group which     is uninterrupted or interrupted by —O—, —S—, or by —NR₇—, and/or is     unsubstituted or substituted by C₁-C₆alkyl; -   R₇ is C₁-C₅alkyl; -   l is from 1 to 4; -   m is from 1 to 7; -   n is from 1 to 4; -   when n=2, R₁, R₅ or R₆ is a bivalent alkyl group; or R₁ and R₂     together with the 2 nitrogen atoms linking them form a —(CH₂)_(m)—     ring; -   when n=3, R₁, R₅ or R₆ is a trivalent alkyl group; -   when n=4, R₁, R₅ or R₆ is a tetravalent alkyl group; and -   R₁ and R₂ in formula (1) are not simultaneously hydrogen.

Preference is given to the use of compounds of formula

(1) or (2a)

wherein

-   R₁ and R₂ are each independently of the other hydrogen; C₁-C₂₂alkyl;     or unsubstituted or C₁-C₅alkyl- or C₁-C₅alkoxy-substituted     C₆-C₂₀aryl; or R₁ and R₂ together with the nitrogen atom linking     them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted     by —O— or by —NH—; -   R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; -   R₄ is a cyano group; —COOR₆; —CONHR₆; —COR₆; or —SO₂R₆; -   R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or     unsubstituted or C₁-C₅alkyl-substituted C₆-C₂₀aryl; or R₅ and R₆     together form a 5- to 7-membered, monocyclic, carbocyclic or     heterocyclic ring; -   Z is a —(CH₂)₁— group which is uninterrupted or interrupted by —O—,     —S—, or by —NR₇—, and/or is unsubstituted or substituted by     C₁-C₆alkyl; -   R₇ is C₁-C₆alkyl; -   l is from 1 to 4; -   m is from 1 to 7; -   n is from 1 to 4; -   when n=2, R₁, R₅ or R₆ is a bivalent alkyl group; or R₁ and R₂     together with the 2 nitrogen atoms linking them form a —(CH₂)_(m)—     ring; -   when n=3, R₁, R₅ or R₆ is a trivalent alkyl group; -   when n=4, R₁, R₅ or R₆ is a tetravalent alkyl group; and -   R₁ and R₂ in formula (1) are not simultaneously hydrogen.

The compounds of formula (1) may be present in the form of E,E-, E,Z- or Z,Z-isomers.

C₁-C₂₂Alkyl denotes a linear or branched, unsubstituted or substituted alkyl group such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, cyclohexyl, n-decyl, n-dodecyl, n-octadecyl, eicosyl, methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N,N-diethylaminopropyl, cyanoethyl, phenethyl, benzyl, p-tert-butylphenethyl, p-tert-octyl-phenoxyethyl, 3-(2,4-di-tert-amylphenoxy)-propyl, ethoxycarbonylmethyl-2-(2-hydroxy-ethoxy)ethyl or 2-furylethyl.

C₁-C₆alkoxy denotes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy.

C₈—C₁₀aryl denotes, for example, phenyl, tolyl, anisyl, mesityl, chlorophenyl, 2,4-di-tert-amylphenyl and naphthyl.

Heterocyclic radicals contain one, two, three or four identical or different ring hetero atoms. Special preference is given to heterocycles which contain one, two or three, especially one or two, identical or different hetero atoms. The heterocycles may be mono- or poly-cyclic, for example mono-, bi- or tri-cyclic. They are preferably mono- or bi-cyclic, especially mono-cyclic. The rings preferably contain 5, 6 or 7 ring members. Examples of monocyclic and bicyclic heterocyclic systems from which radicals occurring in the compounds of formula (1) or (2) may be derived are, for example, pyrrole, furan, thiophene, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, pyran, thiopyran, 1,4-dioxane, 1,2-oxazine, 1,3-oxazine, 1,4-oxazine, indole, benzothiophene, benzofuran, pyrrolidine, piperidine, piperazine, morpholine and thiomorpholine.

When R₅ and R₆ together form a 5- to 7-membered monocyclic carbocyclic or heterocyclic ring, such a ring is, for example, a 1,3-dioxocyclohexane ring such as, for example, a dimedone ring, a 1,3-dioxo-5,5-diethylcyclohexane ring, a 1,3-diaza-2,4,6-trioxocyclohexane ring such as, for example, a barbituric acid ring, a 1,3-dimethylbarbituric acid ring, a 1-phenylbarbituric acid ring, a 1-methyl-3-octylbarbituric acid ring, a 1-ethyl-3-octyloxy-carbonylethylbarbituric acid ring, a 1,2-diaza-3,5-dioxocyclopentane ring such as, for example, a 1,2-diaza-1,2-dimethyl-3,5-dioxocyclopentane ring, a 1,2-diaza-1,2-diphenyl-3,5-dioxocyclopentane ring, or a 2,4-diaza-1-alkoxy-3,5-dioxocyclohexene ring such as, for example, a 2,4-diaza-1-ethoxy-4-ethyl-3,5-dioxocyclohexene ring, a 2,4-diaza-1-ethoxy-4-[3-(2,4-di-tert-amylphenoxy)propyl]-3,5-dioxocyclohexene ring etc.

Preference is given to the use in accordance with the invention of compounds of formula (1) or (2) wherein

-   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)—     ring which is uninterrupted or interrupted by —O— or by —NH—; -   R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; -   R₄ is a cyano group; —COOR₆; —CONHR₆; —COR₆; or —SO₂R₆; -   R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or     C₆-C₂₀aryl; and -   Z is as defined in claim 1.

Amongst those compounds special preference is given to compounds of formula (1) or (2) wherein

-   R₃ is a cyano group; and -   R₄ is —CONHR₆; and -   R₆ is C₁-C₂₂alkyl; or C₆-C₂₀aryl, -   and especially to compounds of formula (1) or (2) wherein -   R₆ is C₄-C₂₀alkyl.

Preference is also given to compounds of formula (1) or (2) wherein

-   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)—     ring which is uninterrupted or interrupted by —O— or by —NH—; -   R₃ is —COOR₅; -   R₄ is a cyano group; —COOR₆; or —SO₂R₆; -   R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or     C₆-C₂₀aryl; and -   m is from 1 to 7.

Amongst those compounds preference is given to those wherein

-   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)—     ring which is uninterrupted or interrupted by —O— or by —NH—; -   R₃ is —COOR₅; -   R₄ is —COOR₆; -   R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or     C₆-C₂₀aryl; and -   m is from 1 to 7; -   and to compounds of formula (1) or (2) wherein -   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)—     ring which is uninterrupted or interrupted by —O— or by —NH—; -   R₃ is —COOR₅; -   R₄ is a cyano group; -   R₅ is C₁-C₂₂alkyl; or C₆-C₂₀aryl; and -   m is from 1 to 7; -   and to compounds of formula (1) or (2) wherein -   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form a —(CH₂)_(m),     ring which is uninterrupted or interrupted by —O— or by —NH—; -   R₃ is —COOR₅; -   R₄ is —SO₂R₆; -   R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or     C₆-C₂₀aryl; and -   m is from 1 to 7.

Preference is further given to the use of compounds of formula

wherein

-   R₁ and R₂ are each independently of the other C₀-C₂₂alkyl; or R₁ and     R₂ together with the 2 nitrogen atoms linking them form a     —(CH₂)_(m)— ring; -   X is —O—; or —NH—; -   Z₂ a —(CH₂)₁— group which is uninterrupted or interrupted by —O—,     —S—, or by —NR₇—, and/or is unsubstituted or substituted by     C₁-C₆alkyl; and -   n is from 1 to 3; -   and especially compounds of formula (3) wherein -   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form the radical

Preference is further given to the use of compounds of formula

wherein

-   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)—     ring which is uninterrupted or interrupted by—O— or by —NH—; -   R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; and -   R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or     C₆-C₂₀aryl; -   and very especially compounds of formula (4) wherein -   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form the radical

Preference is further given to the use of compounds of formula

wherein

-   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)—     ring which is uninterrupted or interrupted by —O— or by —NH—; -   R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; and R₅ is     C₁-C₂₂alkyl; or C₆-C₂₀aryl; -   and very especially compounds of formula (4) wherein -   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and     R₂ together with the nitrogen atom linking them form the radical

Compounds of formula (2) that are preferably used are those wherein

-   Z is an atom grouping which results in the formation of an     oxazolidine ring, a pyrrolidine ring or a thiazolidine ring.

Amongst those compounds very special preference is given to those of formula

wherein

-   R₈ and R₉ are each independently of the other hydrogen; or     C₁-C₅alkyl; and -   Y is —O—; —S—; or —CH₂—;     and -   R₁, R₃, R₄ and n are as defined in claim 1.

Special preference is given to compounds of formula (2a) wherein

-   R₁ is C₁-C₁₂alkyl; -   R₃ is a cyano group; —COOR₅; —CO R₅; or —SO₂R₅; -   R₄ is —COR₆; or —COOR₆; and -   R₅ and R₆ are each independently of the other unsubstituted or     C₁-C₅alkyl- or C₁-C₅alkoxy-substituted C₆-C₂₀aryl.

Further compounds for use in accordance with the invention are listed in Table MC1 hereinbelow:

TABLE MC1 Compound of formula Structure λ_(max) [nm] MC01

362 (MeOH) MC02

374 (MeOH) MC03

372 (MeOH) MC04

361 (MeOH) MC05

362 (MeOH) MC06

374 (MeOH) MC07

375 (EtOH) MC08

373 (MeOH) MC09

370 (MeOH) MC10

362 (MeOH) MC11

375 (MeOH) MC12

392 (MeOH) MC13

380 (MeOH) MC14

392 (MeOH) MC15

384 (MeOH) MC16

390 (MeOH) MC17

385 (MeOH) MC18

384 (MeOH) MC19

373 (MeOH) MC20

389 (MeOH) MC21

374 (MeOH) MC22

395 (MeOH) MC23

378 (EtOH) MC24

388 (MeOH) MC25

395 (MeOH) MC26

374 (MeOH) MC27

385 (MeOH) MC28

373 (MeOH) MC29

383 (MeOH) MC30

385 (MeOH) MC31

394 (MeOH) MC32

387 (MeOH) MC33

375 (MeOH) MC34

383 (MeOH) MC35

374 (MeOH) MC36

385 (MeOH) MC37

372 (MeOH) MC38

372 (MeOH) MC39

380 (EtOH) MC40

Further Merocyanine Derivatives for use in Accordance with the Invention are Listed in Table MC2:

TABLE MC2a

R₁ R₂ R₃ R₄ MC41 C₂H₅ C₂H₅ —COOC₆H₁₃-(n) COOC₆H₁₃-(n) MC42 C₂H₅ C₂H₅ COOC₈H₁₇-(n) COOC₈H₁₇-(n) MC43 C₂H₅ C₂H₅ COOC₈H₁₇-(i) COOC₈H₁₇-(i) MC44 C₂H₅ C₂H₅ COOC₈H₁₇-(i) CN MC45 C₂H₅ C₂H₅ COOC₈H₁₇-(n) CN MC46 C₂H₅ C₂H₅ COOC₁₀H₂₁-(n) CN MC47 C₂H₅ C₂H₅ COOC₁₀H₂₁-(n) SO₂C₆H₆ MC48 C₂H₅ C₂H₅ COOC₁₂H₂₅-(n) CN MC49 C₂H₅ C₂H₅ COOC₁₂H₂₅-(n) SO₂C₆H₆ MC50 C₂H₅ C₂H₅ CN CONHC₈H₁₇-(n) MC51 C₂H₅ C₂H₅ CN CONHC₈H₁₇-(i) MC52 C₂H₅ C₂H₅ CN CONHC₁₀H₂₁-(n) MC53 C₂H₅ C₂H₅ CN CONHC₁₂H₂₅-(n) MC54 C₄H₉-(n) C₄H₉-(n) COOC₄H₉-(n) COOC₄H₉-(n) MC55 C₄H₉-(n) C₄H₉-(n) COOC₆H₁₃-(n) COOC₆H₁₃-(n) MC56 C₄H₉-(n) C₄H₉-(n) COOC₆H₁₃-(n) CN MC57 C₄H₉-(n) C₄H₉-(n) COOC₆H₁₃-(n) SO₂C₆H₆ MC58 C₄H₉-(n) C₄H₉-(n) COOC₈H₁₇-(n) COOC₈H₁₇-(n) MC59 C₄H₉-(n) C₄H₉-(n) COOC₈H₁₇-(n) CN MC60 C₄H₉-(n) C₄H₉-(n) COOC₈H₁₇-(n) SO₂C₆H₆ MC61 C₄H₉-(n) C₄H₉-(n) COOC₈H₁₇-(i) COOC₈H₁₇-(i) MC62 C₄H₉-(n) C₄H₉-(n) COOC₈H₁₇-(i) CN MC63 C₄H₉-(n) C₄H₉-(n) COOC₈H₁₇-(i) SO₂C₆H₈ MC64 C₄H₉-(n) C₄H₉-(n) COOC₁₀H₂₁-(n) CN MC65 C₄H₉-(n) C₄H₉-(n) COOC₁₀H₂₁-(n) SO₂C₆H₆ MC66 C₄H₉-(n) C₄H₉-(n) COOC₁₂H₂₅-(n) CN MC67 C₄H₉-(n) C₄H₉-(n) COOC₁₂H₂₅-(n) SO₂C₆H₆ MC68 C₄H₉-(n) C₄H₉-(n) CN CONHC₆H₁₃-(n) MC69 C₄H₉-(n) C₄H₉-(n) CN CONHC₈H₁₇-(n) MC70 C₄H₉-(n) C₄H₉-(n) CN CONHC₈H₁₇-(n) MC71 C₄H₉-(n) C₄H₉-(n) CN CONHC₁₀H₂₁-(n) MC72 C₄H₉-(n) C₄H₉-(n) CN CONHC₁₂H₂₅-(n) MC73 C₈H₁₇-(i) C₈H₁₇-(i) COOC₄H₉-(n) COOC₄H₉-(n) MC74 C₈H₁₇-(i) C₈H₁₇-(i) COOC₄H₉-(n) CN MC75 C₈H₁₇-(i) C₈H₁₇-(i) COOC₄H₉-(n) SO₂C₆H₆ MC76 C₈H₁₇-(i) C₈H₁₇-(i) COOC₆H₁₃-(n) CN MC77 C₈H₁₇-(i) C₈H₁₇-(i) COOC₆H₁₃-(n) SO₂C₆H₆ MC78 C₈H₁₇-(i) C₈H₁₇-(i) COOC₈H₁₇-(n) CN MC79 C₈H₁₇-(i) C₈H₁₇-(i) COOC₈H₁₇-(n) SO₂C₆H₆ MC80 C₈H₁₇-(i) C₈H₁₇-(i) COOC₈H₁₇-(i) CN MC81 C₈H₁₇-(i) C₈H₁₇-(i) COOC₈H₁₇-(i) SO₂C₆H₆ MC82 C₈H₁₇-(i) C₈H₁₇-(i) CN CONHC₆H₁₃-(n) MC83 C₈H₁₇-(i) C₈H₁₇-(i) CN CONHC₆H₁₇-(n) MC84MC85MC86MC87MC88MC89MC90MC91MC92

COOC₄H₉-(n)COOC₆H₁₃-(n)COOC₈H₁₇-(n)COOC₈H₁₇-(n)COOC₈H₁₇-(n)COOC₈H₁₇-(i)COOC₈H₁₇-(i)COOC₈H₁₇-(i)COOC₁₀H₂₁-(n) COOC₄H₉-(n)COOC₆H₁₃-(n)COOC₈H₁₇-(n)CNSO₂C₆H₆COOC₈H₁₇-nCNSO₂C₆H₆CN MC93MC94MC95MC96MC97MC98MC99MC100MC101

COOC₁₀H₂₁-(n)COOC₁₂H₂₅-(n)COOC₁₂H₂₅-(n)CNCNCNCNCNCN SO₂C₆H₆CNSO₂C₆H₆CONHC₆H₁₃-(n)CONHC₈H₁₇-(n)CONHC₈H₁₇-(i)CONHC₁₀H₂₁-(n)CONHC₁₂H₂₅-(n)CONHC₁₈H₃₇-(n) MC102MC103MC104MC105MC106MC107MC108MC109MC110MC111MC112MC113MC114MC115MC116MC117MC118MC119

COOC₄H₉-(n)COOC₆H₁₃-(n)COOC₈H₁₇-(n)COOC₈H₁₇-(n)COOC₈H₁₇-(n)COOC₈H₁₇-(i)COOC₈H₁₇-(i)COOC₈H₁₇-(i)COOC₁₀H₂₁-(n)COOC₁₀H₂₁-(n)COOC₁₂H₂₅-(n)COOC₁₂H₂₅-(n)CNCNCNCNCNCN COOC₄H₉-(n)COOC₆H₁₃-(n)COOC₈H₁₇-(n)CNSO₂C₆H₆COOC₈H₁₇-(i)CNSO₂C₆H₆CNSO₂C₆H₆CNSO₂C₆H₆CONHC₆H₁₃-(n)CONHC₈H₁₇-(n)CONHC₈H₁₇-(i)CONHC₁₀H₂₁-(n)CONHC₁₂H₂₅-(n)CONHC₁₈H₃₇-(n) MC120

TABLE MC2b

R₁ R₂ X n MC121 C₂H₅ C₂H₅ O 1 MC122 C₂H₅ C₂H₅ O 2 MC123 C₂H₅ C₂H₅ O 3 MC124 C₂H₅ C₂H₅ NH 1 MC125 C₂H₅ C₂H₅ NH 2 MC126 C₂H₅ C₂H₅ NH 3 MC127 C₄H₉-(n) C₄H₉-(n) O 1 MC128 C₄H₉-(n) C₄H₉-(n) O 2 MC129 C₄H₉-(n) C₄H₉-(n) O 3 MC130 C₄H₉-(n) C₄H₉-(n) NH 1 MC131 C₄H₉-(n) C₄H₉-(n) NH 2 MC132 C₄H₉-(n) C₄H₉-(n) NH 3 MC133 C₈H₁₇-(i) C₈H₁₇-(i) O 1 MC134 C₈H₁₇-(i) C₈H₁₇-(i) O 2 MC135 C₈H₁₇-(i) C₈H₁₇-(i) O 3 MC136 C₈H₁₇-(i) C₈H₁₇-(i) NH 1 MC137 C₈H₁₇-(i) C₈H₁₇-(i) NH 2 MC138 C₈H₁₇-(i) C₈H₁₇-(i) NH 3 MC139MC140MC141MC142MC143MC144

OOONHNHNH 123123 MC145MC146MC147MC148MC149MC150

OOONHNHNH 123123

TABLE MC2c

MC151 R₁ R₂ R₃ MC152 C₂H₅ C₂H₅ CN MC153 C₂H₅ C₂H₅ SO₂C₆H₆ MC154 C₄H₉-(n) C₄H₉-(n) CN MC155 C₄H₉-(n) C₄H₉-(n) SO₂C₆H₆ MC156 C₈H₁₇-(i) C₈H₁₇-(i) CN MC157 C₈H₁₇-(i) C₈H₁₇-(i) SO₂C₆H₆ MC158 CN MC159

SO₂C₆H₆ MC160MC161

CNSO₂C₆H₆

TABLE MC2d

Compound R₁ R₂ R₃ MC162 C₂H₅ C₂H₅ CN MC163 C₂H₅ C₂H₅ SO₂C₆H₆ MC164 C₄H₉-(n) C₄H₉-(n) CN MC165 C₄H₉-(n) C₄H₉-(n) SO₂C₆H₆ MC166 C₈H₁₇-(i) C₈H₁₇-(i) CN MC167 C₈H₁₇-(i) C₈H₁₇-(i) SO₂C₆H₆ MC168MC169

CNSO₂C₆H₆ MC170MC171

CNSO₂O₆H₆

TABLE MC2e Compound Structure MC172

MC173

MC174

MC175

MC176

MC177

MC178

MC179

MC180

MC181

MC182

MC183

MC184

MC185

MC186

The spectroscopic data of a number of selected compounds according to the invention are listed in Table MC3:

TABLE MC3 Spectroscopic data of a number of selected compounds according to the invention Compound of formula MW λ_(max) ε E (1%, 1 cm) MC07 403.61 375  66 987 1660 MC37 477.71 371  70 217 1564 MC172 421.60 371  72 697 1724 MC39 306.45 380  62 423 2037 MC173 596.86 390  92 208 1545 MC23 287.45 378  60 076 2090 MC174 552.76 398 146 379 2650 MC187 318.46 382  65 495 2057 MC116 320.44 381  62 217 1942 MC175 225.25 383  68 073 3022 MC177 213.24 373  53 060 2488 MC178 255.27 373  37 684 1476 MC179 253.30 377  49 461 1953 MC180 269.34 378  56 849 2111 MC181 283.33 371  47 704 1684 MC182 325.45 377  60 559 1423 MC183 610.89 386 110 883 2570 370 (sh) MC184 388.56 399 (acetonitrile) MC185 374.57 388 368 (sh) (acetonitrile) MC186 351.45 376 (acetonitrile)

The merocyanine compounds of formula (1) or (2) used in accordance with the invention are, in some cases, known compounds but also include novel compounds.

The novel compounds correspond to formula

wherein

-   R₁ is C₁-C₄alkylene; -   R₂ is C₁-C₅alkyl; or R₁ and R₂ together with the 2 nitrogen atoms     linking them form a —(CH₂)_(m)— ring; -   R₅ is C₁-C₂₂alkyl; and -   m is from 1 to 7.

The UV absorbers according to the present invention can be used either in the dissolved state (soluble organic filters, solubilised organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments).

Any known process suitable for the preparation of microparticles can be used for the preparation of the micronised UV absorbers, for example:

-   -   wet-milling (low-viscosity micronisation process for pumpable         dispersions), with a hard grinding medium, for example zirconium         silicate balls in a ball mill, and a protective surfactant or a         protective polymer in water or in a suitable organic solvent;     -   wet-kneading (high-viscosity micronisation process for         non-pumpable pastes) using a continuous or discontinuous (batch)         kneader. For a wet-kneading process, a solvent (water or         cosmetically acceptable oils), a grinding aid (surfactant,         emulsifier) and a polymeric grinding aid may be used.

Both processes may be used preferably.

-   -   spray-drying from a suitable solvent, for example aqueous         suspensions or suspensions containing organic solvents, or true         solutions in water, ethanol, dichloroethane, toluene or         N-methylpyrrolidone etc.     -   by expansion according to the RESS process (Rapid Expansion of         Supercritical Solutions) of supercritical fluids (e.g. CO₂) in         which the UV filter or filters is/are dissolved, or the         expansion of liquid carbon dioxide together with a solution of         one or more UV filters in a suitable organic solvent;     -   by reprecipitation from suitable solvents, including         supercritical fluids (GASR process=Gas Anti-Solvent         Recrystallisation/PCA process=Precipitation with Compressed         Anti-solvents).

As milling apparatus for the preparation of the micronised organic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill. Even more preferable mills are modern ball mills; manufacturers of these types of mill are, for example, Netzsch (LMZ mill), Drais (DCP-Viscoflow or Cosmo), Buhler AG (centrifugal mills) or Bachhofer. The grinding is preferably carried out with a grinding aid.

Examples of kneading apparatus for the preparation of the micronised organic UV absorbers are typical sigma-blade batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Continua from Werner und Pfleiderer).

Useful low molecular weight grinding aids for all the above micronisation processes are surfactants and emulsifiers as disclosed below in the sections entitled “Emulsifiers”, “Surfactants” and “Fatty alcohols”.

Useful polymeric grinding aids for water dispersion are cosmetically acceptable water-soluble polymers with Mn>500 g/mol, for example: acrylates (Salcare types), modified or non-modified polysaccharides, polyglucosides or xanthan gum. Furthermore an alkylated vinyl-pyrrolidone polymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, Ceteareth-25 or a phospholipid may be used. Oil dispersions may comprise cosmetically acceptable waxy polymers or natural waxes as polymeric grinding aid to adjust the viscosity during and after processing. Examples of other useful polymeric grinding aids are disclosed below in the section entitled “Polymers”.

Useful solvents are water, brine, (poly-)ethylene glycol, glycerol or cosmetically acceptable oils. Other useful solvents are disclosed below in the sections entitled “Esters of fatty acids”, “Natural and synthetic triglycerides, including glyceryl esters and derivatives”, “Pearlescent waxes”, “Hydrocarbon oils” and “Silicones or siloxanes”.

The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2 micrometres, preferably from 0.03 to 1.5 micrometres and more especially from 0.05 to 1.0 micrometres.

The UV absorbers according to the present invention can also be used dry in powder form. For that purpose, the UV absorbers are subjected to known grinding methods, such as vacuum atomisation, countercurrent spray-drying etc. Such powders have a particle size of from 0.1 micrometres to 2 micrometres. To avoid the occurrence of agglomeration, the UV absorbers can be coated with a surface-active compound prior to the pulverisation process, for example with an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or a known polymer, such as PVP, an acrylate etc.

The UV absorbers according to the present invention can also be used in specific carriers for cosmetics, for example in solid lipid nanoparticles (SLN) or in inert sol-gel microcapsules wherein the UV absorbers are encapsulated.

The cosmetic formulations or pharmaceutical compositions according to the present invention can also comprise one or more than one further UV filter as described in Tables 1-3.

The cosmetic or pharmaceutical preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring together the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, for example octyl methoxycinnamate, salicylic acid isooctyl ester etc. The UV absorber can be used, for example, without further treatment, or in the micronised state, or in the form of a powder.

Cosmetic or pharmaceutical preparations contain from 0.05% to 40% by weight, based on the total weight of the composition, of one UV absorber or a mixture of UV absorbers.

Preference is given to the use of mixing ratios of the UV absorber of formula (1) according to the present invention and optional further light-protective agents (as described in Tables 1-3) of from 1:99 to 99:1, especially from 1:95 to 95:1 and preferably from 10:90 to 90:10, based on weight. Of special interest are mixing ratios of from 20:80 to 80:20, especially from 40:60 to 60:40 and preferably approximately 50:50. Such mixtures can be used, inter alia, to improve solubility or increase UV absorption.

The UV absorbers of formula (1) according to the present invention or combinations of UV filters are useful for protecting skin, hair and/or natural or artificial hair colour.

TABLE 1 Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention (The generic scope of the UV absorbers is described in the left-hand column; specific compounds are indicated in the right-hand column) p-aminobenzoic acid derivatives, for example 4-dimethylaminobenzoic acid 2-ethylhexyl ester; salicylic acid derivatives, for example salicylic acid 2-ethylhexyl ester; benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative; diphenylacrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate; 3-imidazol-4-ylacrylic acid and esters; benzofuran derivatives, especially 2-(p-aminophenyl)benzofuran derivatives, described in EP-A-582 189, US-A-5 338 539, US-A-5 518 713 and EP-A-613 893; polymeric UV absorbers, for example the benzylidene malonate derivatives described in EP-A-709 080; cinnamic acid derivatives, for example the 4-methoxycinnamic acid 2-ethylhexyl ester and isoamyl ester or cinnamic acid derivatives described in US-A-5 601 811 and WO 97/00851; camphor derivatives, for example 3-(4′-methyl)benzylidene-bornan-2-one, 3-benzylidene- bornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer, 3-(4′- trimethylammonium)-benzylidene-bornan-2-one methyl sulfate, 3,3′-(1,4-phenylene- dimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic acid) and salts, 3-(4′-sulfo)benzylidene-bornan-2-one and salts; camphorbenzalkonium methosulfate; hydroxyphenyltriazine compounds, for example 2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n- octyloxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]- phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}- 6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine; 2,4-bis{[4-(tris(trimethylsilyloxy- silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2″- methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4- (1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4- methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]- phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine; physical sunscreens, coated or not coated, such as titanium dioxide, zinc oxide, iron oxides, mica, MnO, Fe₂O₃, Ce₂O₃, Al₂O₃, ZrO₂ (surface coatings: polymethylmethacrylate, methicone (methylhydrogenpolysiloxane as described in CAS 9004-73-3), dimethicone, isopropyl titanium triisostearate (as described in CAS 61417-49-0), metal soaps such as magnesium stearate (as described in CAS 4086-70-8), perfluoroalcohol phosphate such as C₉-C₁₅ fluoroalcohol phosphate (as described in CAS 74499-44-8; JP 5-86984; JP 4-330007)). The primary particle size is, on average, 15 nm-35 nm and the particle size distribution is in the range 100 nm-300 nm. aminohydroxy-benzophenone derivatives disclosed in DE 100 11 317, EP 1 133 980 and EP 1 046 391 phenyl-benzimidazole derivatives as disclosed in EP 1 167 358

TABLE 2 Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention DE 10331804 T 1 p 4, T 2 + 3 p 5 EP 613 893 Ex 1-5 + 15, T 1, pp 6-8 EP 1 000 950 Comp. in Table 1, pp 18-21 EP 1 005 855 T 3, p 13 EP 1 008 586 Ex 1-3, pp 13-15 EP 1 008 593 Ex 1-8, pp 4-5 EP 1 027 883 Compound VII, p 3 EP 1 027 883 Comp I-VI, p 3 EP 1 028 120 Ex 1-5, pp 5-13 EP 1 059 082 Ex 1; T 1, pp 9-11 EP 1 060 734 T 1-3, pp 11-14 EP 1 064 922 Compounds 1-34, pp 6-14 EP 1 081 140 Ex 1-9, pp 11-16 EP 1 103 549 Compounds 1-76, pp 39-51 EP 1 108 712 4,5-Dimorph olino-3-hydroxypyridazine EP 1 123 934 T 3, p 10 EP 1 129 695 Ex 1-7, pp 13-14 EP 1 167 359 Ex 1, p 11 and Ex 2, p 12 EP 1 258 481 Ex 1, pp 7, 8 EP 420 707 B1 Ex 3, p 13 (CAS Reg. No 80142-49-0) EP 503 338 T 1, pp 9-10 EP 517 103 Ex 3, 4, 9, 10 pp 6-7 EP 517 104 Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8 EP 626 950 all compounds EP 669 323 Ex 1-3, p 5 EP 780 382 Ex 1-11, pp 5-7 EP 823 418 Ex 1-4, pp 7-8 EP 826 361 T 1, pp 5-6 EP 832 641 Ex 5 + 6 p 7; T 2, p 8 EP 832 642 Ex 22, T 3, pp 10-15; T 4, p 16 EP 852 137 T 2, pp 41-46 EP 858 318 T 1, p 6 EP 863 145 Ex 1-11, pp 12-18 EP 895 776 Comp. in rows 48-58, p 3; R 25 + 33, p 5 EP 911 020 T 2, p 11-12 EP 916 335 T 2-4, pp 19-41 EP 924 246 T 2, p 9 EP 933 376 Ex 1-15, pp 10-21 EP 944 624 Ex 1 + 2, pp 13-15 EP 945 125 T 3 a + b, pp 14-15 EP 967 200 Ex 2; T 3-5, pp 17-20 EP 969 004 Ex 5, T 1, pp 6-8 JP 2000319629 CAS Reg Nos. 80142-49-0, 137215-83-9, 307947-82-6 US 5 635 343 all compounds on pp 5-10 US 5 338 539 Ex 1-9, pp 3 + 4 US 5 346 691 Ex 40, p 7; T 5, p 8 US 5 801 244 Ex 1-5, pp 6-7 WO 0149686 Ex 1-5, pp 16-21 WO 0168047 Tables on pp 85-96 WO 0181297 Ex 1-3, pp 9-11 WO 0238537 All compounds p 3, compounds on rows 1-10 p 4 WO 9217461 Ex 1-22, pp 10-20 WO 9220690 Polymeric Comp in Examples 3-6 WO 9301164 T 1 + 2, pp 13-22 WO 9714680 Ex 1-3, p 10 (Abbreviations T: Table, R: row, Comp: compound, Ex: compound(s) of Patent Example, p: page; the generic scope of the UV absorbers is described in the left-hand column; specific compounds are indicated in the right-hand column)

TABLE 3 Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention (The generic scope of the UV absorbers is described in the left-hand column; specific compounds are indicated in the right-hand column) No. Chemical Name CAS No. 1 (+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo- 36861-47-9 [2.2.1]heptan-2-one 2 1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one 15087-24-8 3 (2-hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone 1641-17-4 4 2,4-dihydroxybenzophenone 131-56-6 5 2,2′,4,4′-tetrahydroxybenzophenone 131-55-5 6 2-hydroxy-4-methoxybenzophenone 131-57-7 7 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid 4065-45-6 8 2,2′-dihydroxy-4,4′-dimethoxybenzophenone 131-54-4 9 2,2′-dihydroxy-4-methoxybenzophenone 131-53-3 10 alpha-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid and its salts 56039-58-8 11 1-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)propane-1,3- 70356-09-1 dione 12 methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2- 52793-97-2 ylidene)methyl]anilinium sulphate; 22 3,3,5-trimethyl-cyclohexyl-2-hydroxy-benzoate 118-56-9 23 isopentyl p-methoxycinnamate 71617-10-2 27 menthyl o-aminobenzoate 134-09-8 28 menthyl salicylate 89-46-3 29 2-ethylhexyl 2-cyano-3,3-diphenylacrylate 6197-30-4 30 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 31 2-ethylhexyl 4-methoxycinnamate 5466-77-3 32 2-ethylhexyl salicylate 118-60-5 33 benzoic acid, 4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-, tris(2- 88122-99-0 ethylhexyl) ester; 2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5- triazine 34 4-aminobenzoic acid 150-13-0 35 benzoic acid, 4-amino-, ethyl ester, polymer with oxirane 113010-52-9 38 2-phenyl-1H-benzimidazole-5-sulphonic acid 27503-81-7 39 2-propenamide, N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2- 147897-12-9 ylidene)methyl]phenyl]methyl]-, homopolymer 40 triethanolamine salicylate 2174-16-5 41 3,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo- 90457-82-2 bicyclo[2.2.1]heptane-1-methanesulfonic acid] 42 titanium dioxide 13463-67-7 44 zinc oxide 1314-13-2 45 2,2′-methylene-bis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl- 103597-45-1 butyl)-phenol] 46 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy- 187393-00-6 phenyl)-(1,3,5)-triazine 47 1H-benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-, 180898-37-7 disodium salt 48 benzoic acid, 4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]- 154702-15-5 phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl) ester 49 phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3- 155633-54-8 tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]- 50 dimethicodiethylbenzalmalonate 207574-74-1 51 benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-, monosodium salt 52 benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexyl ester 302776-68-7 53 1-dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]propyl]- 156679-41-3 N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) 54 1-propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2-propenyl)- 177190-98-6 amino]-, chloride 55 1H-benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis- 170864-82-1 56 1,3,5-triazine, 2,4,6-tris(4-methoxyphenyl)- 7753-12-0 57 1,3,5-triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]- 208114-14-1 58 1-propanaminium, 3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1- 340964-15-0 dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N- methyl-, methyl sulfate (salt) 59 2-propenoic acid, 3-(1H-imidazol-4-yl)- 104-98-3 60 benzoic acid, 2-hydroxy-, [4-(1-methylethyl)phenyl]methyl ester 94134-93-7 61 1,2,3-propanetriol, 1-(4-aminobenzoate) 136-44-7 62 benzeneacetic acid, 3,4-dimethoxy-α-oxo- 4732-70-1 63 2-propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5 64 anthranilic acid, p-menth-3-yl ester 134-09-8 65 2,2′-bis(1,4-phenylene)-1H-benzimidazole-4,6-disulphonic acid 349580-12-7 monosodium salt or disodium phenyl dibenzimidazole tetrasulfonate or Neo-Heliopan AP

Suitable UV filter substances which can additionally be used with the UV absorbers according to the present invention are any UV-A and UV-B filter substances.

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical compositions/preparations according to the invention may also comprise one or one more additional compounds as described below.

Fatty Alcohols

Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10, carbon atoms, including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyidodecanol, benzoates of C₁₂-C₁₅ alcohols, acetylated lanolin alcohol etc.

Esters of Fatty Acids

Esters of linear C₆-C₂₄ fatty acids with linear C₃-C₂₄ alcohols, esters of branched C₆-C₁₃carboxylic acids with linear C₆-C₂₄ fatty alcohols, esters of linear C₆-C₂₄ fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C₆-C₂₂ fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).

Examples of such ester oils are isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl isostearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate etc.

Other Adjuvants

Diethylhexyl 2,6-naphthalate, di-n-butyl adipate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) succinate and diisotridecyl acetate, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate. Esters of C₆-C₂₄ fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C₂-C₁₂dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups, or iminodisuccinic acid and iminodisuccinic acid salts [CAS 7408-20-0] or latex particles.

Natural or Synthetic Triglycerides, Including Glyceryl Esters and Derivatives

Di- or tri-glycerides, based on C₈-C₁₈ fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheatgerm glycerides, etc.). Fatty acid esters of polyglycerol (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc.) or castor oil, hydrogenated vegetable oil, sweet almond oil, wheatgerm oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borage oil etc.

Waxes, including esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g. carnauba wax, beeswax (white or yellow), lanolin wax, candelilla wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl ester wax, synthetic beeswax etc. Also, hydrophilic waxes such as cetearyl alcohol or partial glycerides.

Pearlescent Waxes

Alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof.

Hydrocarbon Oils

Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules such as polydecenes and polybutene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others of vegetable or animal origin.

Silicones or Siloxanes (Organo-substituted Polysiloxanes)

Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear poly-siloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxane volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).

Fluorinated or Perfluorinated Oils

Perfluorohexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethylisopropyl ether.

Emulsifiers

Any conventionally usable emulsifier can be used for the compositions. Emulsifier systems may comprise, for example: carboxylic acids and their salts: alkaline soaps of sodium, potassium and ammonium, metallic soaps of calcium or magnesium, organic-based soaps such as lauric, palmitic, stearic and oleic acid etc. Alkyl phosphates or phosphoric acid esters, acid phosphates, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethylene glycol esters, PEG-n acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched, from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol of propylene oxide with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycol ethers such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycol ethers such as PEG-n-stearate, PEG-n-oleate, PEG-n-cocoate. Monoglycerides and polyol esters. C₁₂-C₂₂ fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol esters such as glycerol monostearate, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycol esters such as diethylene glycol monostearate, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucrose esters, glycerol and saccharose esters such as sucrose glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquilsostearate, sorbitan, PEG-(6)-sorbitan isostearate, PEG-(10)-sorbitan laurate, PEG-17-sorbitan dioleate. Glucose derivatives, C₈-C₂₂alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcoholvcetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated paraffins, sulfonated tetrapropylene sulfonate, sodium lauryl sulfates, ammonium and ethanolamine lauryl sulfates, lauryl ether sulfates, sodium laureth sulfates, sulfosuccinates, acetyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine derivatives, amine salts, ethoxylated amines, oxly amines with chains containing a heterocycle, such as alkyl imidazolines, pyridine derivatives, isoquinolines, cetylpyridinium chloride, cetylpyridinium bromide, quaternary ammonium such as cetyltrimethylammonium bromide (CTBA), stearylalkonium. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxydiamides. Polysiloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene). Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethyl-ammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobetaines. Alkylimidazolines, alkyl peptides, lipoamino acids, self-emulsifying bases and the compounds as described in K. F. DePolo, A short textbook of cosmetology, Chapter 8, Table 8-7, p 250-251.

Non-ionic emulsifiers such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl 2-isostearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [Arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate [Arlacel 1689], sorbitan stearate and sucrose cocoate [Arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and Ceteth-20 [cetomacrogol wax], cetearyl alcohol and polysorbate 60 and PEG-150 and stearate-20 [polawax GP 200, polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1 OOONI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 and steareth-10 [emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate [Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N21], PEG6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].

Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl alcohol and sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phosphate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.

The emulsifiers may be used in an amount of, for example, from 1 to 30% by weight, especially from 4 to 20% by weight and preferably from 5 to 10% by weight, based on the total weight of the composition.

When formulated in O/W emulsions, the preferred amount of such emulsifier systems may constitute 5% to 20% of the oil phase.

Adjuvants and Additives

The cosmetic/pharmaceutical preparations, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition comprise, as further adjuvants and additives, mild surfactants, superfatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colorants, bacteria-inhibiting agents and the like.

Superfatting Agents

Substances suitable for use as superfatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers.

Surfactants

Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isothionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.

Consistency Regulators/Thickeners and Rheology Modifiers

Silicon dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, carragheenan, gellan, pectins, or modified cellulose such as hydroxycellulose, hydroxypropyl methylcellulose. In addition polyacrylates or homopolymers of crosslinked acrylic acids and polyacrylamides, carbomers (Carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez 10) or the Salcare range such as Salcare SC80 (steareth-10 allyl ether/acrylate copolymer), Salcare SC81 (acrylate copolymer), Salcare SC91 and Salcare AST (sodium acrylate copolymer/PPG-1 trideceth-6), Sepigel 305 (polyacrylamide/laureth-7), Simulgel NS and Simulgel EG (hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylate/vinyl isodecanoate crosspolymer), Pemulen TR-1 (acrylate/C₁₀-C₃₀alkyl acrylate crosspolymer), Luvigel EM (sodium acrylate copolymer), Aculyn 28 (acrylate/beheneth-25 methacrylate copolymer) etc.

Polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternised vinylpyrrolidone/vinyl imidazole polymers, for example Luviquat® (BASF), condensation products of polyglycols and amines, quatemised collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolysed collagen (Lamequat®L/Grünau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyl diethylene-triamine (Cartaretin/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as microcrystals; condensation products of dihaloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1, Mirapol AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleateAsobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncross-linked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyl-trimethylammonium chloride/acrylate copolymers, octyl acrylamide/methyl methacrylate-tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinyl-pyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore, the polymers as described in EP 1 093 796 (pages 3-8, paragraphs 17-68) may be used.

Biogenic Active Ingredients

Biogenic active ingredients are to be understood as meaning, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Deodorising Active Ingredients

As deodorising active ingredients there come into consideration, for example, anti-perspirants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron® of Hoechst AG, Frankfurt (FRG), there is available commercially, for example, an aluminium chlorohydrate corresponding to formula Al₂(OH)₅Cl×2.5H₂O, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxy-acetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Henkel), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-phenol (Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also proved especially effective.

Anti-dandruff Agents

As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyrithione.

Film Formers

Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.

Antioxidants

In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that interrupt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such anti-oxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes, lycopene and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]sulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof (e.g. selenium methionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS (=“Hindered Amine Light Stabilizers”) compounds may also be mentioned. Further synthetic and natural antioxidants are listed e.g. in patent WO 0025731: structures 1-3 (page 2), structure 4 (page 6), structures 5-6 (page 7) and compounds 7-33 (page 8-14).

The amount of antioxidants present is usually from 0.001 to 30% by weight, preferably from 0.01 to 3% by weight, based on the weight of the UV absorber of formula (1).

Hydrotropic Agents

To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether; diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical-grade oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical-grade diglycerol mixtures having a diglycerol content of from 40 to 50% by weight; methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanol-amine or 2-amino-1,3-propanediol.

Preservatives and Bacteria-inhibiting Agents

Suitable preservatives include, for example, methyl, ethyl, propyl and butyl parabens, benzalkonium chloride, 2-bromo-2-nitro-propane-1,3-diol, dehydroacetic acid, diazolidinyl urea, 2-dichloro-benzyl alcohol, DMDM hydantoin, formaldehyde solution, methyldibromo-glutanitrile, phenoxyethanol, sodium hydroxymethylglycinate, imidazolidinyl urea, triclosan and further substance classes listed in the following reference: K. F. DePolo—A short textbook of cosmetology, Chapter 7, Table 7-2,7-3, 7-4 and 7-5, p 210-219.

Bacteria-inhibiting Agents

Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlor-hexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4′-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2% by weight, based on the solids content of the preparations.

Perfume Oils

There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.

Colorants

There may be used as colorants the substances that are suitable and permitted for cosmetic purposes, as compiled, for example, in the publication “Kosmetische Färbemittel” of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. The colorants are usually used in concentrations of from 0.001 to 0.1% by weight, based on the total mixture.

Other Adjuvants

It is furthermore possible for the cosmetic preparations to comprise, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or styrene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N₂O, dimethyl ether, CO₂, N₂ or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.

Suitable insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose.

Polymeric Beads or Hollow Spheres as SPF Enhancers

The combination of the UV-absorbers and UV-absorber combinations, listed above, with SPF enhancers, such as non-active ingredients like styrene/acrylate copolymers, silica beads, spheroidal magnesium silicate, crosslinked polymethylmethacrylates (PMMA; Micopearl M305 Seppic), can maximize the UV protection of the sun products. Hollow-sphere additives (Sunspheres® ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore increased (EP 0 893 119). Some beads, as mentioned previously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g. Micropearl M305, can modulate skin-shine by eliminating reflection phenomena and may indirectly scatter the UV light.

Cosmetic or Pharmaceutical Preparations

Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:

-   -   skin-care preparations, e.g. skin-washing and cleansing         preparations in the form of tablet-form or liquid soaps,         soapless detergents or washing pastes;     -   bath preparations, e.g. liquid (foam baths, milks, shower         preparations) or solid bath preparations, e.g. bath cubes and         bath salts;     -   skin-care preparations, e.g. skin emulsions, multi-emulsions or         skin oils;     -   cosmetic personal care preparations, e.g. facial make-up in the         form of day creams or powder creams, face powder (loose or         pressed), rouge or cream make-up, eye-care preparations, e.g.         eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix         creams; lip-care preparations, e.g. lipsticks, lip gloss, lip         contour pencils, nail-care preparations, such as nail varnish,         nail varnish removers, nail hardeners or cuticle removers;     -   foot-care preparations, e.g. foot baths, foot powders, foot         creams or foot balsams, special deodorants and antiperspirants         or callus-removing preparations;     -   light-protective preparations, such as sun milks, lotions,         creams or oils, sunblocks or tropicals, pre-tanning preparations         or after-sun preparations;     -   skin-tanning preparations, e.g. self-tanning creams;     -   depigmenting preparations, e.g. preparations for bleaching the         skin or skin-lightening preparations;     -   insect-repellents, e.g. insect-repellent oils, lotions, sprays         or sticks;     -   deodorants, such as deodorant sprays, pump-action sprays,         deodorant gels, sticks or roll-ons;     -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;     -   preparations for cleansing and caring for blemished skin, e.g.         synthetic detergents (solid or liquid), peeling or scrub         preparations or peeling masks;     -   hair-removal preparations in chemical form (depilation), e.g.         hair-removing powders,     -   liquid hair-removing preparations, cream- or paste-form         hair-removing preparations, hair-removing preparations in gel         form or aerosol foams;     -   shaving preparations, e.g. shaving soap, foaming shaving creams,         non-foaming shaving creams, foams and gels, preshave         preparations for dry shaving, aftershaves or aftershave lotions;     -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de         toilette, eau de parfum, parfum de toilette, perfume), perfume         oils or perfume creams;     -   cosmetic hair-treatment preparations, e.g. hair-washing         preparations in the form of shampoos and conditioners, hair-care         preparations, e.g. pretreatment preparations, hair tonics,         styling creams, styling gels, pomades, hair rinses, treatment         packs, intensive hair treatments, hair-structuring preparations,         e.g. hair-waving preparations for permanent waves (hot wave,         mild wave, cold wave), hair-straightening preparations, liquid         hair-setting preparations, hair foams, hairsprays, bleaching         preparations, e.g. hydrogen peroxide solutions, lightening         shampoos, bleaching creams, bleaching powders, bleaching pastes         or oils, temporary, semi-permanent or permanent hair colourants,         preparations containing self-oxidising dyes, or natural hair         colourants, such as henna or camomile.         Presentation Forms

The final formulations listed may exist in a wide variety of presentation forms, for example:

-   -   in the form of liquid preparations as a W/O, OMw, OMw/O, W/O/W         or PIT emulsion and all kinds of microemulsions,     -   in the form of a gel,     -   in the form of an oil, a cream, milk or lotion,     -   in the form of a powder, a lacquer, a tablet or make-up,     -   in the form of a stick,     -   in the form of a spray (spray with propellent gas or pump-action         spray) or an aerosol,     -   in the form of a foam, or     -   in the form of a paste.

Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of special interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.

Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition: from 0.01 to 5% by weight of a UV absorber according to the invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% by weight of sodium chloride, and water ad 100%.

For example, especially the following hair-cosmetic formulations may be used:

-   a₁) spontaneously emulsifying stock formulation, consisting of the     UV absorber according to the invention, PEG-6-C₁₀oxoalcohol and     sorbitan sesquioleate, to which water and any desired quaternary     ammonium compound, for example 4% minkamidopropyl     dimethyl-2-hydroxyethylammonium chloride or Quaternium 80, is added; -   a₂) spontaneously emulsifying stock formulation consisting of the UV     absorber according to the invention, tributyl citrate and     PEG-20-sorbitan monooleate, to which water and any desired     quaternary ammonium compound, for example 4% minkamidopropyl     dimethyl-2-hydroxyethylammonium chloride or Quaternium 80, is added; -   b) quat-doped solutions of the UV absorber according to the     invention in butyl triglycol and tributyl citrate; -   c) mixtures or solutions of the UV absorber according to the     invention with n-alkylpyrrolidone.

Other typical ingredients in such formulations are preservatives, bactericides and bacterio-static agents, perfumes, dyes, pigments, thickening agents, moisturising agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.

Examples of Cosmetic and Pharmaceutical Preparations (X=Preferred Combinations)

O/W systems: Ingredients 1 2 3 4 5 6 7 8 Emulsifiers Potassium cetyl phosphate 2%-5% X Cetearyl alcohol/dicetyl phosphate/ X ceteth-10 phosphate 2%-6% Sodium stearyl phthalamate X 1%-2% Cetearyl alcohol/behentrimonium X methosulfate 1%-5% Quaternium-32 1%-5% X Dimethicone copolyol/caprylic/ X capric triglyceride 1%-4% Steareth-2/steareth-21 2%-5% X Polyglyceryl methyl glucose X distearate 1%-4% Lipophilic emollient/ X X X X X X X X dispersant oil 15%-20% Fatty alcohols and/or X X X X X X X X waxes 1%-5% Thickeners (water-swellable X X X X X X X X thickeners) 0.5%-1.5% Preservatives 0.5%-1% X X X X X X X X Chelating agents (such X X X X X X X X as EDTA) 0%-0.2% Antioxidants 0.05%-0.2% X X X X X X X X Water, deionised, q.s. 100% X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X UV absorber according X X X X X X X X to the invention 0.1%-20% UV absorber as described X X X X X X X X in Tables 1-3 0%-30%

W/O systems Ingredients 1 2 3 4 5 Emulsifiers X X X X X Polyglyceryl-2 dipolyhydroxystearate 2%-4% X X X X X PEG-30 dipolyhydroxystearate 2%-4% X Rapeseed oil sorbitol esters 1%-5% X PEG-45/dodecyl glycol copolymer 1%-5% X Sorbitan oleate/polycerol-3 ricinoleate 1%-5% X Lipophilic emollient/dispersant oil 10%-20% X X X X X Fatty alcohols and/or waxes 10%-15% X X X X X Electrolytes (NaCl, MgSO₄) 0.5%-1% X X X X X Polyol phase (propylene glycol, glycerol) 1%-8% X X X X X Preservatives 0.3%-0.8% X X X X X Perfume oils 0.1%-0.4% X X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X X Antioxidants 0.05%-0.2% X X X X X Water, deionised, q.s. 100% X X X X X UV absorber according to the X X X X X invention 0.1%-20% UV absorber as described X X X X X in Tables 1-3 0%-30%

W/silicone systems Ingredients 1 2 3 4 Emulsifiers Dimethicone copolyol/cyclomethicone 5%-10% X X Laurylmethicone copolyol 5%-10% X X Silicone phase Cyclopentasiloxane 15%-25% X X Dimethicone 15%-25% X X Silicone elastomer Dimethicone/vinyldimethicone crosspolymer 1%-10% X X X X Humectant/polyols (propylene glycol, glycerol . . . ) X X X X 2%-8% Chelating agents (such as EDTA) 0%-0.2% X X X X Antioxidants 0.05%-0.2% X X X X Preservatives 0.3%-0.8% X X X X Perfume oils 0.1%-0.4% X X X X Water, deionised q.s. 100% X X X X UV absorber according to the invention 0.1%-20% X X X X UV absorber as described in Tables 1-3 0%-30% X X X X

Multiple emulsions Ingredients 1 2 3 4 5 6 7 8 9 10 11 12 Primary emulsion W1/O PEG-30 dipolyhydroxystearate X X X 2%-6% Cetyl dimethicone copolyol X X 1%-3% PEG-30 dipolyhydroxystearate/ X X steareth-2/steareth-21 4%-6% Polyglyceryl-2 dipolyhydroxy- X X stearate 1%-3% Polyglyceryl-6 ricinoleate X X X 1%-3% Oil phase 15%-30% Fatty acid esters X X X X X X X Natural and synthetic triglycerides X X X X X X X Hydrocarbon oils X X X X X X X Silicone oils X X X X X X X Preservatives 0.3%-0.8% X X X X X X X X X X X X Water, deionised, q.s. 100% X X X X X X X X X X X X Ionic monofunctional O/W emulsifiers Sorbitan stearate/sucrose cocoate X X X 3%-7% Sucrose laurate 3%-7% X X X Poloxamer 407 3%-7% X X X Polyoxyethylene (20) sorbate X X X monoleate 3%-5% Primary emulsion W1/O 50% X X X X X X X X X X X X Thickeners (water-swellable X X X X X X X X X X X X polymers) 0.3%-1% Water, deionised, q.s. 100% X X X X X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X X X X X UV absorber according to the X X X X X X X X X X X X invention 0.1%-20% UV absorber as described in X X X X X X X X X X X X Tables 1-3 0%-30%

O1/W/O2 emulsions Ingredients 1 2 3 4 5 6 7 8 Primary emulsion O1/W PEG-60 hydrogenated X X X X castor oil 25% Steareth-25 25% X X X X Oil phase 75% Fatty acid esters X X Natural and synthetic triglycerides X X Hydrocarbon oils X X Silicone oils X X Preservatives 0.3%-0.8% X X X X X X X X Water, deionised, q.s. 100% X X X X X X X X Non-ionic multifunctional W/O X X X X X X X X emulsifier 2%-5% Waxes 1%-5% X X X X X X X X Oil phase 20%-30% X X X X X X X X Fatty acid esters Natural and synthetic triglycerides Hydrocarbon oils Silicone oils Primary emulsion O1/W 15% X X X X X X X X Electrolytes (NaCl, MgSO₄) X X X X X X X X 0.1%-0.5% Water, deionised, q.s. 100% X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X UV absorber according to the X X X X X X X X invention 0.1%-20% UV absorber as described in X X X X X X X X Tables 1-3 0%-30%

Microemulsions Ingredients 1 2 3 4 5 6 7 8 9 10 Surfactants PEG-8 caprylic/capric X X X X X glycerides 10%-25% PPG-5-ceteth-20 X X X X X 10%-25% Co-surfactants Polyglyceryl-6 X X isostearate 5%-15% Polyglyceryl-3 X X diisostearate 5%-15% Polyglyceryl-6 X X dioleate 5%-15% PPG-10 cetyl ether X X 5%-15% Ethoxydiglycol 5%-15% X X Oil phase 10%-80% X X X X X X X X X X Isostearyl benzoate X X X X X X X X X X Isostearyl isostearate X X X X X X X X X X PEG-7 glyceryl cocoate X X X X X X X X X X Cyclomethicone X X X X X X X X X X Polyalcohols/ X X X X X X X X X X humectants 1%-10% Preservatives 0.3-0.8% X X X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X X X Water, deionised, X X X X X X X X X X q.s. 100% UV absorber according X X X X X X X X X X to the invention 0.1%-20% UV absorber as described X X X X X X X X X X in Tables 1-3 0%-30%

O/W spray emulsions Ingredients 1 2 3 4 5 6 Emulsifiers Alkyl phosphates 0.1%-5% X X X Glucosidic derivatives 0.1%-5% X X X Solubilisers Ethoxylated glyceryl ethers 0.1%-1% X X Polysorbates 0.1%-1% X X Ethoxylated oleyl ethers 0.1%-1% X X Film-forming agents PVP/VA copolymer 1%-10% X X X PVM/MA copolymer 1%-10% X X X Oil phase 5%-20% X X X X X X Natural oils (meadowfoam, jojoba, X X X X X X macadamia . . . ) Fatty acids esters X X X X X X Mineral oils X X X X X X Silicone oils X X X X X X Alcohol 0%-50% X X X X X X Thickeners 0.1%-0.5% X X X X X X Polyacrylates X X X X X X Aluminium/magnesium silicates X X X X X X Gums X X X X X X Neutralising agents 0%-1% X X X X X X Polyalcohols/humectants 1%-5% X X X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X X X Antioxidants 0.05%-0.2% X X X X X X Water, deionised, q.s. 100% X X X X X X Perfume oils 0.1%-0.5% X X X X X X Preservatives 0.4%-1% X X X X X X UV absorber according to the invention X X X X X X 0.1%-20% UV absorber as described in Tables X X X X X X 1-3 0%-30%

G - Aqueous Ingredients 1 2 3 4 5 6 7 8 9 10 11 12 Thickeners Natural thickener 1%-5% X X X X Semi-synthetic thickener X X X X 1%-5% Synthetic thickener 0.3%-1.3% X X X X Neutralising agents 0.5%-1.5% X X X X X X X X X X X X Polyols - humectants 5%-50% X X X X X X X X X X X X Film-forming agent/conditioner Polyquaternium series 1%-5% X X X X X X PVM/MA copolymer 1%-5% X X X X X X Preservatives 0.5%-1% X X X X X X X X X X X X Chelating Agents (as EDTA) X X X X X X X X X X X X <0.1% Water, deionised, q.s. 100% X X X X X X X X X X X X Perfume oils 0.05%-0.4% X X X X X X X X X X X X Solubilisers Ethoxylated glyceryl ethers X X X 0.1%-5% Polysorbates 0.1%-5% X X X Ethoxylated oleyl ethers X X X X X X 0.1%-5% UV absorber according to the X X X X X X X X X X X X invention 0.1%-20% UV absorber as described in X X X X X X X X X X X X Tables 1-3 0%-30%

Oleogels Ingredients 1 2 3 4 5 6 7 8 9 10 Thickeners Hydrogenated X X lecithin 1%-10% Silica dimethyl X X silylate 1%-10% Silica 1%-5% X X C₂₄₋₂₈Alkyl X X dimethicone 1%-5% Aluminium or X X magnesium stearate 1%-5% Polyols - humectants X X X X X X X X X X 5%-70% Oil phase 20%-90% Dicaprylyl ether X X X Phenyl trimethicone X X Hydrogenated X polyisobutene Isopropyl isostearate X X Oleogel base (mineral X X oil and hydrogenated butylene/ethylene or ethylene/propylene styrene copolymer) Silicone wax 1%-10% X X X X X X X X X X Dimethiconol behenate X X X X X X X X X X Dimethiconol stearate X X X X X X X X X X Perfume oils 0.1%-0.5% X X X X X X X X X X Antioxidants X X X X X X X X X X 0.05%-0.2% UV absorber according X X X X X X X X X X to the invention 0.1%-20% UV absorber as X X X X X X X X X X described in Tables 1-3 0%-30%

Light/dry cosmetic oils Ingredients 1 2 3 4 Lipophilic base Hydrocarbon oils 30%-70% X X Fatty acid esters, branched or unbranched 10%-50% X X Light-feel agent Silicones/siloxanes 0%-10% X X Perfluorinated oils and perfluoroethers 0%-10% X X Viscosifying agents 0%-10% X X X X Waxes Esters of long-chain acids and alcohols 0%-2% X X X X Antioxidants 0.1%-1% X X X X Solubilisers/dispersing agents 0%-5% X X X X Perfume oils 0.1%-0.5% X X X X UV absorber according to the invention 0.1%-20% X X X X UV absorber as described in Tables 1-3 0%-30% X X X X

Foaming/mousse products Ingredients SD Alcohol 40 0%-8% X Propellant 8%-15% X Nonionic emulsifier/surfactant 0.5%-3% X Corrosion Inhibitor 0%-1% X Perfume oils 0.1%-0.5% X Preservatives 0.1%-1% X Miscellaneous 0%-1% X UV absorber according to the invention 0.1%-20% X UV absorber as described in Tables 1-3 0%-30% X

Stick products Ingredients Waxes 15%-30% X Natural and silicone oils 20%-75% X Lanolin derivatives 5%->50% X Esters of lanolin x Acetylated lanolin x Lanolin oil x Colorants and pigments 10%-15% X Antioxidants 0.1%-0.8% X Perfume oils 0.1%-2% X Preservatives 0.1%-0.7% X UV absorber according to the invention 0.1%-20% X UV absorber as described in Tables 1-3 0%-30% X

Liquid and compact Ingredients 1 2 Liquid foundation Powder phase 10%-15% X Oil phase 30%-40%; 75% (only for anhydrous X form) Thickener/suspending agents 1%-5% X Film-forming polymers 1%-2% X Antioxidants 0.1%-1% X Perfume oils 0.1%-0.5% X Preservatives 0.1%-0.8% X Water, deionised, q.s. 100% X Compact powder Powder phase 15%-50% X Oil phase 15%-50% X Polyol phase 5%-15% X Antioxidants 0.1%-1% X Perfume oils 0.1%-0.5% X Preservatives 0.1%-0.8% X For the two product forms UV absorber according to the invention 0.1%-20% X X UV absorber as described in Tables 1-3 0%-30% X X

Conditioning Shampoos Ingredients 1 Primary surfactants (listed previously) 5%-10% X Secondary surfactants (listed previously) 5%-15% X Foam stabilisers (listed previously) 0%-5% X Water, deionised, 40%-70% X Actives 0-10% X Conditioners x Refatting agents x Moisturising agents x Thickeners/rheology modifiers 0%-3% X Humectants 0%-2% X pH-adjusting agents 0%-1% X Preservatives 0.05%-1% X Perfume oils 0.1%-1% X Antioxidants 0.05%-0.20% X Chelating agents (EDTA) 0%-0.2% X Opacifying agents 0%-2% X UV absorber according to the invention 0.1%-20% X UV absorber as described in Tables 1-3 0%-30% X

In the Examples that follow, percentages are based on weight.

PREPARATION EXAMPLES Example 1 Preparation of the Compound of Formula

N-(3-Anilino-allylidene)-aniline (4.5 g, 0.02 mol) and cyanoacetic acid 2-ethylhexyl ester (4.2 g, 0.021 mol) are stirred in 10 ml of acetanhydride for 2 hours at 85-90° C. After removing the excess of acetanhydride in vacuo, the reaction batch is poured onto ice, and the resulting precipitate is filtered off and washed with copious amounts of water. After drying in vacuo at 60° C., the intermediate product is taken up in 10 ml of dry ethanol, and diethylamine (3.1 g, 0.042 mol) is added. The reaction mixture is stirred for 2 hours at 50-55° C. The ethanol and the excess of amine are then distilled off in vacuo. The residue, in a mixture of toluene and acetone (9.5:0.5), is subjected to fractionated filtration over silica gel 60 from Merck and isolated. The pure product is dried under a high vacuum at 60° C. Yield: 4.5 g (73.5% of theory).

Example 2 Preparation of the Compound of Formula

N-(3-Anilino-allylidene)-aniline (4.5 g, 0.02 mol) and cyanoacetic acid 2-ethylhexyl ester (4.2 g, 0.021 mol) are stirred in 10 ml of acetanhydride for 2 hours at 85-90° C. After removing the excess of acetanhydride in vacuo, the reaction batch is poured onto ice, and the resulting precipitate is filtered off and washed with copious amounts of water. After drying in vacuo at 60° C., the intermediate product is taken up in 10 ml of dry ethanol, and diethyl-1,3-propanediamine (1.3 g, 0.01 mol) is added.

The reaction mixture is stirred for 2 hours at 50° C. The ethanol is then distilled off, and the residue, in a mixture of toluene and acetone (9:1), is subjected to fractionated filtration over silica gel 60 from Merck and isolated. The pure product is then dried in vacuo at 60° C. Yield: 4.4 g (73% of theory).

Example 3 Preparation of the Compound of Formula

N-(3-Anilino-allylidene)-aniline (4.5 g, 0.02 mol) and cyanoacetic acid 2-ethylhexyl ester (4.2 g, 0.021 mol) are stirred in 10 ml of acetanhydride for 2 hours at 85-90° C. After removing the excess of acetanhydride in vacuo, the reaction batch is poured onto ice, and the resulting precipitate is filtered off and washed with copious amounts of water. After drying in vacuo at 60° C., the intermediate product is taken up in 10 ml of dry ethanol, and piperazine (0.8 g, 0.01 mol) is added. After stirring for 2 hours at 50-55° C., the ethanol is distilled off in vacuo. Subsequent column chromatography over silica gel 60 from Merck using a mixture of toluene and acetone (9:1) yields the pure product, which is dried in vacuo at 60° C. Yield: 3.9 g (69% of theory).

APPLICATION EXAMPLES Example 4 O/W Emulsion

(A): UV absorber of formula (101)   3 g sesame oil  10 g glyceryl stearate   4 g stearic acid   1 g cetyl alcohol 0.5 g polysorbate 20 0.2 g

(B): propylene glycol 4 g propylparaben 0.05 g methylparaben 0.15 g triethanolamine 0.1 g carbomer 934 0.1 g water ad 100 ml Preparation of the Emulsion Phase (A):

Firstly, the UV absorber is dissolved in sesame oil. The other components of (A) are added thereto and combined.

Phase (B):

Propylparaben and methylparaben are dissolved in propylene glycol. 60 ml of water are then added, heating to 70° C. is carried out and then carbomer 934 is emulsified therein.

Emulsion:

(A) is slowly added to (B) with vigorous application of mechanical energy. The volume is adjusted to 100 ml by the addition of water.

Example 5 Daily Care Cream, Type O/W

% w/w INCI name (as used) Part A Glyceryl stearate (and) cetearyl alcohol 4.0 (and) cetyl palmitate (and) cocoglycerides Ceteareth-12 4.0 Cetearyl alcohol 2.0 Dicaprylyl ether 4.5 Ethylhexyl stearate 4.0 Hexyl laurate 3.5 Ethylhexyl triazone 1.0 Benzylidene malonate polysiloxane 2.0 HDI/trimethylol hexyl-lactone 5.0 crosspolymer (and) silica Stearyl dimethicone 1.0 Dimethicone 2.0 Cetyl alcohol 0.8 compound of formula (101) 2.0 Part B Water q.s. to 100 Water (and) scleroglucan (and) phenoxyethanol 2.0 Glycerol 2.0 Part C Steareth-10 allyl ether/acrylate copolymer  0.45 Phenoxyethanol (and) methylparaben (and) 0.7 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Aqua (and) tocopheryl acetate (and) caprylic/capric 4.0 triglyceride (and) polysorbate 80 (and) lecithin Part E Water (and) sodium hydroxide q.s. Fragrance q.s. Preparation Procedure: Part A and part B are heated separately to 80° C. Part A is poured into part B, whilst stirring continuously. Afterwards the mixture is homogenized with an Ultra Turrax at 11 000 rpm for 20 sec. The mixture is cooled to 60° C. and part C is added. At a temperature below 30° C., part D is added and the pH value is adjusted with sodium hydroxide to between 6.5 and 7.0. Finally, fragrance is added.

Example 6 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 compound of formula (101a) 2.0 Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0 Part E Water (and) sodium hydroxide q.s. Fragrance q.s. Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. The mixture is cooled to 60° C. and part C and part D are incorporated. The mixture Is homogenised again for a short time (5 sec./11 000 rpm) and further cooled, with moderate stirring. At room temperature, the pH is adjusted with sodium hydroxide solution to between 5.5 and 6.0. Finally, fragrance is added.

Example 7 Daily Care UV-protection Lotion

% w/w INCI name (as used) Part A Oleth-3 phosphate 0.6 Steareth-21 2.5 Steareth-2 1.0 Cetyl alcohol 0.8 Stearyl alcohol 1.5 Tribehenin 0.8 Isohexadecane 8.0 compound of formula (101) 5.0 Part B Water q.s. to 100 Glycerol 2.0 Methylene bis-benzotriazolyl tetramethylbutylphenol 3.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Disodium EDTA 0.1 Part C Water 20.0 Diazolidinyl urea (and) iodopropynyl 0.15 butylcarbamate Propylene glycol 4.0 Part D Sodium acrylate copolymer (and) liquid 1.5 paraffin (and) PPG-1 trideceth-6 Cyclopentasiloxane 4.5 PEG-12 dimethicone 2.0 Tocopheryl acetate 0.45 Water (and) citric acid q.s. Part E Fragrance q.s. Preparation Procedure

Heat part A and part B separately to 75° C. Pour part A into part B, whilst stirring continuously. Immediately after emulsification, incorporate in the mixture SF 1202 and SF 1288 from part D. Afterwards homogenise with an Ultra Turrax at 11 000 rpm for 30 sec. Allow to cool to 65° C. and incorporate SALCARE SC91. At a temperature below 50° C., add part C. At 35° C. or below, incorporate vitamin E acetate and subsequently adjust the pH with citric acid. At room temperature, add part E.

Example 8 Sun-protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 compound of formula (101) 2.0 Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodium hydroxide q.s. Fragrance q.s. Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. The mixture is cooled to 60° C., and part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11 000 rpm). After further cooling, with moderate stirring, the pH is adjusted with sodium hydroxide at room temperature. A solution between pH 5.50 and 6.00 is obtained. Finally, fragrance is added.

Example 9 Sun-protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 Mixture of the compound of formula 2.0 (101) (50%) and Uvinul A Plus CAS Reg. No. 302776-68-7 (50%) Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodium hydroxide q.s. Fragrance q.s. Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. After cooling 60° C., part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11 000 rpm). After further cooling, with moderate stirring, the pH is adjusted at room temperature with sodium hydroxide solution to between 5.50 and 6.00. Finally, fragrance is added.

Example 10 Sun-protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 Mixture of compound of formula (101) 2.0 (50%) and benzylidene camphor, CAS Reg. No. 36861-47-9 (50%) Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodium hydroxide q.s. Fragrance q.s. Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. After cooling to 60° C., part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11 000 rpm). After further cooling, with moderate stirring, the pH is adjusted at room temperature with sodium hydroxide. A solution between pH 5.50 and 6.00 is obtained. Finally, fragrance is added. 

1. A method of protecting human and animal hair or skin from UV radiation, which comprises contacting said hair or skin with an effective UV-protective amount of a compound of formula

wherein R₁ and R₂ are each independently of the other hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; —SO₂R₅; or —CONR₁R₅; R₄ is a cyano group; —COOR₆; —CONHR₆; —COR₆; —SO₂R₆; or —CONR₂R₆; R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C₆alkyl-substituted C₆-C₂₀aryl; or R₃ and R₄ together or R₅ and R₆ together form a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; Z₁ and Z₂ are each independently of the other a —(CH₂)₁— group which is uninterrupted or interrupted by —O—, —S—, or by —NR₇—, and/or is unsubstituted or substituted by C₁-C₆alkyl; R₇ is C₁-C₅alkyl; l is a number from 1 to 4; m is a number from 1 to 7; n is a number from 1 to 4; when n=2, R₁, R₅ or R₆ is a bivalent alkyl group; or R₁ and R₂ together with the 2 nitrogen atoms linking them form a —(CH₂)_(m)— ring; when n=3, R₁, R₅ or R₆ is a trivalent alkyl group; when n=4, R₁, R₅ or R₆ is a tetravalent alkyl group; and R₁ and R₂ in formula (1) are not simultaneously hydrogen.
 2. A method according to claim 1, relating to a compound of formula (1) or (2a)

wherein R₁ and R₂ are each independently of the other hydrogen; C₁-C₂₂alkyl; or unsubstituted or C₁-C₅alkyl- or C₁-C₅alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; R₄ is a cyano group; —COOR₆; —CONHR₆; —COR₆; or —SO₂R₆; R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or unsubstituted or C₁-C₅alkyl-substituted C₆-C₂₀aryl; or R₅ and R₆ together form a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; Z₁ and Z₂ are each independently of the other a —(CH₂)_(l)— group which is uninterrupted or interrupted by —O—, —S—, or by —NR₇—, and/or is unsubstituted or substituted by C₁-C₅alkyl; R₇ is C₁-C₅alkyl; l is a number from 1 to 4; m is a number from 1 to 7; n is a number from 1 to 4; when n=2, R₁, R₅ or R₆ is a bivalent alkyl group; or R₁ and R₂ together with the 2 nitrogen atoms linking them form a —(CH₂)_(m)— ring; when n=3, R₁, R₅ or R₆ is a trivalent alkyl group; when n=4, R₁, R₅ or R₆ is a tetravalent alkyl group; and R₁ and R₂ in formula (1) are not simultaneously hydrogen.
 3. A method according to claim 1, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; R₄ is a cyano group; —COOR₆; —CONHR₆; —COR₆; or —SO₂R₆; R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or C₆-C₂₀aryl; and Z is as defined in claim
 1. 4. A method Use according to claim 1, wherein R₃ is a cyano group; and R₄ is —CONHR₆; and R₆ is C₁-C₂₂alkyl; or C₆-C₂₀aryl.
 5. A method according to claim 1, wherein R₆ is C₄-C₂₀alkyl.
 6. A method according to claim 1, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is —COOR₅; R₄ is a cyano group; —COOR₆; or —SO₂R₆; R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or C₆-C₂₀aryl; and m is from 1 to
 7. 7. A method according to claim 6, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is —COOR₅; R₄ is —COOR₆; R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or C₆-C₂₀aryl; and m is from 1 to
 7. 8. A method according to claim 6, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is —COOR₅; R₄ is a cyano group; R₅ is C₁-C₂₂alkyl; or C₆-C₂₀aryl; and m is from 1 to
 7. 9. A method according to claim 6, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is —COOR₅; R₄ is —SO₂R₆; R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or C₆-C₂₀aryl; and m is from 1 to
 7. 10. A method according to claim 1, which comprises using a compound of formula

wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the 2 nitrogen atoms linking them form a —(CH₂)_(m)— ring; X is —O—; or —NH—; Z₂ is a —(CH₂)_(l)— group which is uninterrupted or interrupted by —O—, —S—, or by —NR₇—, and/or is unsubstituted or substituted by C₁-C₆alkyl; and n is a number from 1 to
 3. 11. A method according to claim 10, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form the radical


12. A method according to claim 1, which comprises using a compound of formula

wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; and R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; or C₆-C₂₀aryl.
 13. A method according to claim 12, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form the radical


14. A method according to claim 1, which comprises using a compound of formula

wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; and R₅ is C₁-C₂₂alkyl; or C₆-C₂₀aryl.
 15. A method according to claim 14, wherein R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or R₁ and R₂ together with the nitrogen atom linking them form the radical


16. A method according to claim 1, wherein Z₁ or Z₂ is an atom grouping which results in the formation of an oxazolidine ring, a pyrrolidine ring or a thiazolidine ring.
 17. A method according to claim 16, wherein the compound corresponds to formula

wherein R₈ and R₉ are each independently of the other hydrogen; or C₁-C₅alkyl; Y is —O—; —S—; or —CH₂—; R₁ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ together with the nitrogen atom linking them form a —(CH₂)_(m)— ring which is uninterrupted or interrupted by —O— or by —NH—; R₃ is a cyano group; —COOR₅; —CONHR₅; —COR₅; or —SO₂R₅; —CONR₁R₅; R₄ is a cyano group; —COOR₆; —CONHR₆; —COR₆; or —SO₂R₆; —CONR₂R₆; R₅ and R₆ are each independently of the other C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C₆alkyl-substituted C₆-C₂₀aryl; or R₃ and R₄ together or R₅ and R₆ together form a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; and n is a number from 1 to
 4. 18. A method according to claim 17, wherein R₁ is C₁-C₁₂alkyl; R₃ is a cyano group; —COOR₅; —COR₅; or —SO₂R₅; R₄ is —COR₆; or —COOR₆; R₅ and R₆ are each independently of the other unsubstituted or C₁-C₅alkyl- or C₁-C₅alkoxy-substituted C₆-C₂₀aryl.
 19. A cosmetic preparation comprising at least one or more compounds of formula (1) or (2) according to claim 1 with cosmetically acceptable carriers or adjuvants. 